Publication Type : Journal Article
Publisher : New J. Chem., The Royal Society of Chemistry
Source : New J. Chem., The Royal Society of Chemistry, Volume 44, p.3350-3365 (2020)
Url : http://dx.doi.org/10.1039/C9NJ05166J
Campus : Amritapuri
School : School of Arts and Sciences
Department : Chemistry
Year : 2020
Abstract : The work reveals that a chelate-type interaction in the transition state of a β-aminoalkyl radical in a copper(i)-catalyzed 5-exo-trig radical cyclization step changes the usual stereochemistry of the NH-pyrrolidine ring predicted by the Beckwith–Houk transition state model. In contrast, the rigidity in the fused β-aminoalkyl radical changes the Baldwin's predicted 5-exo to 6-endo cyclization mode, preferentially forming a piperidine ring over a pyrrolidine ring via a geometrically constrained transition state. The resultant diverse NH-pyrrolidines, pyrrolines and piperidines are sources of the bioactive natural product roseophilin and the drug Ritalin among others.
Cite this Research Publication : Sandhya Sadanandan and Gupta, D. Kumar, “Changing stereoselectivity and regioselectivity in copper(i)-catalyzed 5-exo cyclization by chelation and rigidity in aminoalkyl radicals: synthesis towards diverse bioactive N-heterocycles”, New J. Chem., vol. 44, pp. 3350-3365, 2020.
